CN1032444A - Make polyacrylate polymers sulfurized vulcanization process without issue - Google Patents
Make polyacrylate polymers sulfurized vulcanization process without issue Download PDFInfo
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- CN1032444A CN1032444A CN88106893A CN88106893A CN1032444A CN 1032444 A CN1032444 A CN 1032444A CN 88106893 A CN88106893 A CN 88106893A CN 88106893 A CN88106893 A CN 88106893A CN 1032444 A CN1032444 A CN 1032444A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
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Abstract
A kind of usefulness two component vulcanization systems or unite the polyacrylic rubber sulfurized vulcanization process without issue that contain halogen and the two sulfuration points of carboxyl that make that a components system realizes.Two component vulcanization systems comprise the hydrochlorate of one or more metals and quaternary ammonium salt and (or) season salt.One component vulcanization system comprises the hydrochlorate of quaternary ammonium or season .Till this method comprises vulcanizing agent and polyacrylic rubber blend and the composition of gained is heated to sulfuration.Because mixed composition has good preservation stability, therefore baking immediately.This method can also comprise the step of mixed composition stores when needs vulcanize.
Description
The application be submitted on September 28th, 1987, U.S.'s file number be 101,883, autograph is the part continuation application of the patent application of " making polyacrylate polymers sulfurized vulcanization process without issue ".
The present invention be used to make the polyacrylic ester sulfurized vulcanization process without issue that contains two sulfuration points (dual cure sites) relevant.This vulcanization system comprises and replaces ammonium and (or the quaternary salt of) Phosphonium also comprises the acid acceptor that resembles an alkali metal salt and so on sometimes.Vulcanization process without issue of the present invention is unique, because polyacrylic rubber has stability in storage extremely for a long time when being mixed with an amount of vulcanizing agent (curative), is lower than temperature range limit as long as keep its temperature.When the people will vulcanize the polyacrylate polymers that is mixed with vulcanizing agent in interior,, just can achieve the goal as long as temperature is brought up in the temperature range limit.
For example, it is well-known making the polyacrylate polymers sulfurized certain methods that contains two sulfuration points with quaternary ammonium salt as ripening agent.Below three United States Patent (USP)s be to make polyacrylic ester sulfurized typical method.
The United States Patent (USP) 3,875,092 of Morris discloses and has used quaternary ammonium salt to make unique vulcanizing agent, and sulfuration contains the acrylic elastomer of fontanel element and carboxyl sulfuration point.Composition after the sulfuration has good physical properties, low press vulcanization and postcure compression set.
People's such as Morris United States Patent (USP) 3,912,672 discloses a kind of vulcanization system that is used for two sulfuration point acrylic elastomers.This acrylic elastomer has plain and two kinds of sulfurations of the carboxyl point of fontanel, is an alkali metal salt sulfurized with a kind of carboxylic acid or organic phosphoric acid.An alkali metal salt can be sodium stearate or potassium stearate.This sulfuration can also be added with quaternary amine or amine, with the catalyst vulcanization effect.
People's such as Morris United States Patent (USP) 3,976,610 discloses a kind of alkali-metal carboxylate salt of a kind of use or organophosphate and a kind of amine blocked isocyanate, and sulfurized contains the acrylic elastomer of fontanel element and the two sulphur centers of carboxyl.Basic metal can be sodium stearate or potassium stearate.As other vulcanizable polyacrylate composition, these compositions also have low press vulcanization and postcure compression set.
None addresses vulcanization process without issue above-mentioned patent, does not also recognize the influence of temperature limitation to polyacrylic rubber.Following patent has been spoken of the possibility of vulcanization process without issue briefly.
People's such as Yagishite United States Patent (USP) 4,650,834 has been introduced a kind of vulcanizable elastomer that contains a kind of epoxy group(ing) as sulphur center.This vulcanizable epoxy elastomerics also contains the carboxylic acid that has at least two carboxyls in a kind of molecule.But be used to make elastomerics sulfurized vulcanizing agent quaternary ammonium salt Huo quaternary alkylphosphonium salt.Though the present invention proposes that the possibility of saving the postcure stage is arranged, none saves the precedent in postcure stage.And above-mentioned referenced patent is not mentioned the stability in storage that shuts and the problem of temperature limitation aspect fully.
More than some typical vulcanization process of mentioning in these referenced patent all need about 15～20 hours postcure time, even the method that people such as Yagishita propose also needs the postcure time with 16 hours.Acrylic elastomer has the oil-proofness that good weathering resistance, good high temperature suitability are become reconciled.These good properties make this class rubber can be used for automotive field and non-automotive field, for example industry and field application.The use of this class rubber has been subjected to the restriction of vulcanized rubber postcure in use tendency.This causes the rotten and goods be full of cracks in some cases of goods.In order to solve these difficult problems, often expressly propylene sulfide acid esters rubber was reached 24 hours or postcure for more time, to reach than sulfuration more completely.This point can obtain proof from the compression set minimizing.Reduce or save the needed time of postcure industry is had very big benefit.Another advantage of acrylic compound is to have extended storage stability.In the past, resemble the method for the method, steam method, continuous sulfurizing sulfurization technology and the like of pressure moulding and injection moulding or transfer molding and so on, all be subjected to vulcanizing slowly and the bad restriction of stability in storage.The invention solves these difficult problems.
Making the polyacrylic ester sulfurized vulcanization process without issue that contains two sulfuration points, is to realize with a component vulcanization system of two special component vulcanization systems or associating.Two component vulcanization systems comprise metal acid-salt, particularly sodium stearate and potassium stearate, and the ammonium and (or the quaternary salt of) Phosphonium of alkyl replacement.Polyacrylic rubber must have the plain and two sulfuration of the carboxyl point of fontanel.Ammonium and (or the structural formula of) phosphonium salt is as follows:
In the formula: Q is nitrogen or phosphorus; R
1, R
2, R
3And R
4Be alkyl; X is that organic acid or the negatively charged ion of mineral acid, the especially X that acidic hydrogen is connected with fontanel element or Sauerstoffatom is fontanel element or alkyl, alkaryl or alkoxyl group carboxylic acid, phosphoric acid and vitriolic acidic group.
As mentioned above, two component vulcanization systems comprise a kind of hydrochlorate and a kind of quaternary salt of metal.Can think, when two component vulcanization systems be mix and react the time, negatively charged ion that quaternary salt produces and the reaction of the hydrochlorate of metal, formation season hydrochlorate.Following reaction formula is represented the situation of an embodiment.
The stearic acid quaternary ammonium
So, if quaternary salt is the hydrochlorate as above-mentioned regulation, a component vulcanization system also be can be used for of the present invention.X for example
-Can be RCOO
-And C preferably
17H
35COO
-
In a broad sense, the present invention includes a kind of usefulness have hydrochlorate (as the hydrochlorate or the organophosphate of metal) and ammonium and (or) vulcanization system of the quaternary salt of Phosphonium, make and contain the plain and bicentric polyacrylic ester elastomerics of the carboxyl sulfurized vulcanization process without issue of fontanel.Specific practice is: be lower than under the limit or the activation temperature scope in temperature, said components is mixed into uniform composition: then this composition is heated to activation or temperature range limit or surpasses this scope, so that the sulfuration of polyacrylic ester elastomerics.Quaternary salt can be the hydrochlorate that resembles stearate and so on.
Vulcanization system without issue of the present invention and vulcanizable acrylic elastomer are to contain one or more acrylate monomers, a kind of plain monomer of active fontanel and a kind of interpolymer that contains carboxylic monomer of containing.
Acrylic elastomer contain account for the about 40～99.8%(weight of polymer weight) structural formula acrylate as follows:
R is the alkyl that contains 1-8 carbon atom in the formula, contains the alkoxyalkyl or the alkane alkylthio of 2～12 left and right sides carbon atoms.The structure of alkyl can comprise primary, the configuration of the second month in a season and tertiary carbon.The example of this class acrylate is: methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, isobutyl acrylate, vinylformic acid pentyl ester, vinylformic acid isopentyl ester, Ethyl acrylate, propylene ester 2-methyl pentyl ester, Octyl acrylate, 2-EHA, decyl acrylate, dodecylacrylate and vinylformic acid octadecane ester or the like; Vinylformic acid methoxy methyl esters, vinylformic acid methoxy ethyl ester, vinylformic acid ethoxy ethyl ester, vinylformic acid fourth 2-ethoxyethyl acetate, vinylformic acid ethoxy propyl ester, vinylformic acid first sulfo-ethyl ester and vinylformic acid second sulfo-ethyl ester or the like; Vinylformic acid α, beta-cyano ethyl ester, vinylformic acid α, beta-cyano propyl ester, vinylformic acid δ cyano group propyl ester, vinylformic acid cyano group butyl ester, the own ester of vinylformic acid cyano group and vinylformic acid cyano group monooctyl ester or the like.Usually can with two or more monomers and (or) mixture of two or more type acrylate monomers.
This rubber should contain about 65～99.6%(weight) structural formula such as above-mentioned acrylate.R is the alkoxyalkyl that contains the alkyl of 1～10 left and right sides carbon atom or contain 2～8 left and right sides carbon atoms in the formula.The example of more desirable acrylate is: ethyl propenoate, propyl acrylate, butyl acrylate, Ethyl acrylate, 2-EHA and Octyl acrylate or the like; With vinylformic acid methoxy ethyl ester and vinylformic acid ethoxy ethyl ester or the like.Can use alkyl acrylate and alkyl acrylate oxyalkyl ester simultaneously.
This rubber contains 0.1～30%(weight of having an appointment) contain the plain monomer of active fontanel.The fontanel element can be chlorine, bromine or iodine.The monomeric example of this class is, the Mono Chloro Acetic Acid vinyl ester, the bromoacetic acid vinyl ester, the Mono Chloro Acetic Acid allyl ester, the chloropropionic acid vinyl ester, the chloro-butyric acid vinyl ester, the bromo-butyric acid vinyl ester, vinylformic acid 2-chloroethene ester, vinylformic acid 3-chlorine propyl ester, vinylformic acid 4-neoprene ester, methacrylic acid 2-chloroethene ester, vinylformic acid 2-bromine ethyl ester, vinylformic acid 2-iodo-ethyl ester, 2-chloroethyl vinyl ether, the chloromethyl vinyl ketone, vinylformic acid 4-chloro-crotyl ester, vinyl chloride, 5-chloromethyl norbornylene, 5-(α-Mono Chloro Acetic Acid ylmethyl)-and 2-norbornylene and 5-(α, β-dichloropropylene acidic group methyl)-the 2-norbornylene or the like.The most desirable monomer is Mono Chloro Acetic Acid vinyl ester, Mono Chloro Acetic Acid allyl ester, vinylformic acid 2-chloroethene ester, 2-chloroethyl vinyl ether, vinyl chloride, 5-chloromethyl-2-norbornylene and 5-Mono Chloro Acetic Acid ylmethyl-2-norbornylene.
This rubber better is to contain about 0.2～15%(weight) contain the plain monomer of active fontanel.Under this content, the content of fontanel element is about 0.1～5%(weight of rubber mass).Because use value and cost, chloride monomer is the most desirable.
This rubber also contains 0.1～20%(weight of having an appointment) contain carboxylic monomer.This monomer can be monocarboxylic acid or the poly carboxylic acid that contains 3～8 left and right sides carbon atoms.The monomeric example of this class is vinylformic acid, methacrylic acid, ethylacrylic acid, β, beta dimethylacrylic acid, Ba Dousuan, 2-valeric acid, 2-caproic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, 3-butene-1,2,3-tricarboxylic acid and the like.
This rubber better is to contain 0.2～10%(weight) about contain carboxylic monomer.Under this content, carboxyl-content is 0.1～7%(weight of rubber mass) about.Comparatively desirable monomer is that the earnest of the quiet of ヴ people's cape ヌ thin silk fabric ┧ curtain ⒓ ┧ Min ostrich donkey Deng cape magpie is got
This rubber can contain up to about 35%(preferably up to about 10%) (weight) contain vinylidene (
But) vinylidene monomer of other copolymerization of end group.The monomeric example of this class is: phenyl acrylate, cyclohexyl acrylate and methyl acrylic ester, for example methyl methacrylate and Jia Jibingxisuanyizhi or the like; Vinyl and allylic ester class, for example vinyl-acetic ester, vinyl propionate base ester and allyl acetate or the like; Vinyl ketones, for example methyl vinyl ketone; Vinyl and allylic ethers, for example methoxy ethylene, ethyl vinyl ether and allyl group methyl ether or the like; Vinyl aromatic (co) hydro carbons, for example vinylbenzene, alpha-methyl styrene and Vinyl toluene or the like; Vinyl nitrile, for example vinyl cyanide and methacrylonitrile; Vinylamide class, for example acryl acid amides, methacryloyl acid amides and N-methyl acryl acid amides or the like; Dienes and divinyl class, for example divinyl, isoprene, Vinylstyrene, divinyl ether and diethylene glycol diacrylate or the like.Comparatively desirable copolymerisable monomer is vinyl-acetic ester, methyl methacrylate, Jia Jibingxisuanyizhi, vinylbenzene, vinyl cyanide, acryl acid amides, Vinylstyrene and diethylene glycol diacrylate.
Acrylic elastomer can be prepared with polymerization techniques such as the known emulsion of professional (latex), suspension, solution and bodies.Because wish when polymerization, to have 90% or more conversion of monomer, so normally adopt emulsion and suspension polymerization technique.Polymerization can be undertaken by intermittent reaction operation, perhaps in preparation process one or several component is cooperated pari passu and reacts.The temperature range of polyreaction is comparatively desirable with about 5～80 ℃ temperature range for-10～100 ℃ of pacts.
Can use the radical initiator initiated polymerization.The example of this initiator is: organic peroxide and hydroperoxide type, for example secondary methane of benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide and hydroperoxidation or the like uses separately or uses with redox system; Diazonium compound class, for example Diisopropyl azodicarboxylate etc.; Persulphate, for example Sodium Persulfate, Potassium Persulphate and ammonium persulphate use separately or use with redox system; With the UV-light of using with photosensitizers, the example of photosensitizers is benzophenone, triphenyl phosphine and organic diazonium class or the like.
Typical letex polymerization component will comprise persulphate or organo-peroxide, general redox system, the pH value of acid or alkali is adjusted to water and technical well-known negatively charged ion, positively charged ion or the nonionogenic tenside of the required water that meets the requirements, general buffering inorganic salt.
Polyreaction will proceed to monomeric transformation efficiency usually and reach till about 90%.The latex of gained (if adopting emulsion method) can be told polymkeric substance by condensing.Coagulation method commonly used is salt-acid cure connection and freezing coagulation.The used salt of salt-acid cure connection is for resembling sal epsom (MgSO
4) or the polyvalent metal salt of calcium chloride and so on, used alcohol is the alcohol of pure and mild Virahol of weevil and so on.The rubber of gained generally need wash with water and is dry thus.
The stock polymer of acrylic elastomer has about 20～100 Mooney point (ML-4,212).
With general equipment (for example Banbury closed mixing machine and extrusion machine etc.) this rubber is mixed with component and matching component with sulfuration.
During the preparation vulcanisable compound, available Banbury closed mixing machine or other general-purpose equipment make polymkeric substance mix with vulcanizing agent.Except vulcanization system and polymkeric substance, also can comprise technical general carbon black, other filler, antioxidant, emulsifying agent, softening agent, inhibitor and promotor of generally all knowing or the like in the vulcanisable compound.
Two component vulcanization systems of the present invention comprise a kind of hydrochlorate of metal and ammonium and (or the quaternary salt of) Phosphonium that a kind of alkyl replaces.The hydrochlorate of metal can be carboxylate salt and the organophosphate that contains 2～24 left and right sides carbon atoms.The structural formula of this organophosphate is:
（R-O）zPOyM
In the formula: M is a basic metal; Y equals 1 or 2; Z equals 1 or 2; Y adds z and equals 3; R is selected from the group of being made up of alkyl that contains 1～24 left and right sides carbon atom and the aryl that contains 6～24 left and right sides carbon atoms.The example of the hydrochlorate of the metal of particularly suitable comprises: carboxylate salt, for example stearate, acetate, butyrates, lauroleate, palmitate, oleate, benzoate; And organophosphate, for example alkane phenoxy group many (vinyl oxygen base) ethyl phosphate.More specific hydrochlorate comprises sodium stearate, potassium stearate, copper stearate or similar salt.
The replacement ammonium is with (or the quaternary salt of) Phosphonium is all 4 salt that hydrogen atom is replaced by organic radical entirely in the An Huo Phosphonium.The structure of quaternary ammonium salt Huo quaternary alkylphosphonium salt is:
Wherein: Q is nitrogen or phosphorus; R
1, R
2, R
3And R
4For containing the alkyl of 1～18 left and right sides carbon atom, for example alkyl, aryl, alkaryl, aralkyl, or R
1, R
2, R
3And R
4In 2 or 3 form the heterocycle structure that contains 3～8 atoms with nitrogen or phosphorus atom, the group that this 3～8 atom selects free carbon, nitrogen, oxygen and sulphur to form, having 2 atoms in the heterocycle structure at least is carbon atoms; X is that organic acid or the negatively charged ion of mineral acid, particularly X that acidic hydrogen is connected with fontanel element or Sauerstoffatom is fontanel element or alkyl, alkaryl or alkoxyl group carboxylic acid, phosphoric acid and vitriolic acidic group.The example of more specific this anionoid comprises chlorine (Cl
-), bromine (Br
-), iodine (I
-) or oxyhydroxide (OH
-), sulfuric acid (HSO
- 4), phosphoric acid (H
2PO
- 4) carboxylic acid (RCOO
-), organic sulfuric acid (ROSO
- 3Or RSO
- 3) and organic phosphoric acid (ROPO
3H
-).R in last several examples is for containing 1～18 left and right sides carbon atom alkyl or alkaryl.
In a component vulcanization system of the present invention, not that the hydrochlorate of employing metal and the quaternary salt of An Huo Phosphonium must be the hydrochlorates of carboxylic acid or organic phosphoric acid.Exactly, vulcanizing agent is that quaternary ammonium Huo quaternary phosphine contains 2～24 left and right sides carbon atom carboxylic acid's salt or structural formula organophosphate as follows.
（R-O）zPOyM
In the formula: M is a quaternary ammonium Huo quaternary phosphine; Y equals 1 or 2; Z equals 1 or 2; Y adds z and equals 3; R is selected from the group of being made up of alkyl that contains 1～24 left and right sides carbon atom and the aryl that contains 6～24 left and right sides carbon atoms.In a part of vulcanization system, X is preferably RCOO
-Shown ion, that more suitable is C
17H
35COO
-The structural formula of the stearate of the most desirable quaternary ammonium Huo quaternary phosphine is:
In the formula: Q is nitrogen or phosphorus; R
1, R
2, R
3And R
4Same as described above.
The example that is used for the quaternary ammonium salt of two component vulcanization systems is a tetramethylammonium chloride, tetramethylammonium bromide, iodate trimethylammonium second ammonium, chloro trimethylammonium soya-bean oil base (soya) ammonium, bromination trimethylammonium cetyltrimethyl ammonium, the chlorination benzyl trimethyl ammonium, chlorination dimethyl second ammonium, chlorination dimethyl octyl group benzyl ammonium, chlorination dimethyl oil base (oleyl) benzyl ammonium, chlorination dimethyl stearyl benzyl ammonium, bromination 3,5-dimethylphenyl benzyl ammonium, bromination dimethyl dibenzyl ammonium, methyl chloride ethyl propyl isobutyl ammonium, Tetradecyltrimethylammonium chloride, Diethylaminoethyl hexadecyl dibenzyl ammonium, cetylpyridinium chloride, dodecyl bromide pyridine, TBAC tetrabutylammonium chloride, the bromination tetrabutylammonium, tetrabutylammonium iodide, the tetramethylammonium hydroxide pentahydrate, bromination hexadecyl methyl second ammonium, tosic acid hexadecyl TMA (TriMethylAmine) and tetradecyl trimethylammonium bromide or the like.
The example that is used for two component vulcanization system De quaternary alkylphosphonium salts is Xiuization Si Ben Phosphonium, bromination Shi six alkyl San Ding Phosphonium, Lvization Si Ben Phosphonium, iodate Si Ben Phosphonium, Lvization Si Ding Phosphonium, Xiuization Si Ding Phosphonium, chlorinated triphenyl Ji Bian Phosphonium, bromination triphenyl Bian Phosphonium, iodate triphenyl Bian Phosphonium, chlorinated triphenyl ylmethoxy Jia Phosphonium, Lvization San Yi Ji Bian Phosphonium and chlorination thricyclohexyl Bian Phosphonium or the like.
Example as the hydrochlorate of the quaternary ammonium Huo quaternary phosphine of a component vulcanizing agent is the stearic acid benzyl trimethyl ammonium, stearic acid San Jia Ji Bian Phosphonium, stearic acid trimethylammonium soya-bean oil base (soya) ammonium, stearic acid trimethylammonium soya-bean oil Ji Phosphonium, the stearic acid tetramethylammonium, stearic acid Si Jia Phosphonium, stearic acid hexadecyl TMA (TriMethylAmine), stearic acid Shi six Wan base San Jia Phosphonium, the stearic acid tetrabutylammonium, stearic acid 3,5-dimethylphenyl benzyl ammonium, stearic acid 3,5-dimethylphenyl Bian Phosphonium and alkyl acid phosphate phenoxy group many (vinyloxy group) ethyl ester or the like.
Can use these quaternary ammonium salts Huo quaternary alkylphosphonium salt by single form or by the form of mixture of two or more.The consumption of quaternary ammonium salt Huo quaternary alkylphosphonium salt is generally per 100 weight parts, 0.1～20 weight part, preferably 1～4 weight part.In two component vulcanization systems, the amount ranges of the hydrochlorate of metal is per 100 parts by weight polymer, 0.1～10 weight part, preferably 2～6 weight parts.When making the vulcanisable compound sulfuration, select above-mentioned amount ranges, can make hardenable compositions reach high sulfuration or vulcanization rate with good mechanical properties and compression set, have good processing stability and extended storage stability.If the consumption of the hydrochlorate of metal and quaternary salt is lower than specialized range, sulfuration or curing are carried out very slowly so, almost do not have sulfuration.Otherwise, if the hydrochlorate of metal and quaternary salt surpass above-mentioned scope, sulfuration and solidification rate are exceedingly fast, making does not have process period and crosses the drought sulfuration.In addition, mechanical properties and compression set also degenerate greatly.
As mentioned above, can said components be mixed with the general-purpose equipment that resembles Banbury closed mixing machine and so on.
As an aspect of of the present present invention, the composition that is used for present method has " ultimate temperature characteristic ".The meaning of this speech of ultimate temperature characteristic is that composition just can maintain its stability in storage over a long time once acquisition as long as this vulcanizable composition is in to be lower than under the ultimate temperature uniformly.But this composition one stands ultimate temperature, just can vulcanize quite rapidly and fully, so that not need the postcure step.Or rather, little this result of long-time interior composition MV minium viscosity variation shows as long as this composition remains below under the ultimate temperature, will have quite low vulcanization rate.Specifically, the inventive method is to be lower than 150 mooney units after making the MV minium viscosity of vulcanisable compound be changed to for 2 weeks, preferably be lower than 5 mooney units [under 100 ℃, the measured value of mooney's viscosimeter ectotrochanter test method(s) (Mooney Viscometer Large Rotor Test) ASTM D1646] after 8 weeks.But this composition one stands ultimate temperature, just can vulcanize quite rapidly.The standard of " ultimate temperature " is that (ASTM D1646) records t with mooney's viscosimeter ectotrochanter test method(s)
5Value increased or temperature more for a long time at 5 in 31 minutes.And, according to the present invention, sulfuration more fully under the temperature of temperature that oversteps the extreme limit, so that do not need the postcure step.The sign of finishing vulcanisation step without the postcure step of prior art is, 150 ℃ and overlapped following 70 hours after compression set (ASTM test method(s) D 395) for being equal to or less than 80%, preferably be equal to or less than 40%.
The ultimate temperature of the hydrochlorate of various metals and the mixture of quaternary salt is different.But, as long as have stability in storage just two best component vulcanizing agents are kept to be lower than about 50 ℃.In general, for the vulcanizing agent of the best, temperature range limit is approximately 90～150 ℃.When surpassing 150 ℃, most of vulcanisable compound utmost point promptly vulcanizes and vulcanized drought so that can't process.
If surpass above-mentioned a certain optimum range and can accelerate vulcanization rate widely, if adopt general acrylate with inhibitor then can enlarge the upper limit of above-mentioned scope though the front has been mentioned used sulfuration dosage.If the use inhibitor can make vulcanization rate reduce.But if use excessive greatly vulcanizing agent because of a large amount of inhibitor makes, though vulcanization rate is reduced, the physical properties of resulting polymers is very bad.When using very small amount of inhibitor, can obtain fabulous physical properties.The general inhibitor that is used for polyacrylate polymers is an acids, for example citric acid, acetate and stearic acid or the like.
Embodiment 1
Present embodiment is the stability in storage that is used for illustrating vulcanisable compound.Under room temperature (25 ℃), following component is mixed with the Banbury closed mixing machine.
Based on per hour
Form 100 weight part explanations
Polyacrylic rubber 100 has chlorine and the two sulfurations of carboxyl
The polyacrylic ester of point
Stearic acid 1 inhibitor, lubricant
The ester of Struktol WB-222 2 saturated fatty acids, behaviour
Make auxiliary agent
N 550, FEF 75 carbon black fillers
Agerite* Stalits S 2 octylated diphenylamines, antioxygen
Change agent
Thiokol TP-759 6 ethers/ester, softening agent
Add up to 186 weight parts
5 parts of vulcanizing agents (i.e. 4 weight part sodium stearate and 1 weight part CETRIMIDE POWDER) are added in 186 parts of total mixtures, have altogether 191 weight part vulcanisable compounds.With two-roller mill with the composition mixing after, be determined at mooney viscosity under 93 ℃ and 125 ℃ with ectotrochanter.After this also carry out the 8 weeks test of same vulcanisable compound, keep sample under room temperature (25 ℃) at duration of test.At duration of test, redeterminated the mooney viscosity of vulcanisable compound under 93 ℃ and 125 ℃.Measurement result such as following table.These results show that Mooney during 8 weeks (ectotrochanter) viscosity change is very little, therefore show to have extended storage stability.
Mooney viscosity (ectotrochanter)
93 ℃ of 8 all aged at room temperature of 93 ℃ of former primary states
Former state is refined former state again and is refined
MV minium viscosity 62 49 69 45
t
5, minutes 23.5 16.75＞31 16
t
35, minute＞31＞31＞31＞31
Mooney viscosity (ectotrochanter)
125 ℃ of 8 all aged at room temperature of 125 ℃ of former primary states
Former state is refined former state again and is refined
MV minium viscosity 65 52 74 44
t
5Minutes 2.5 2.25 3.5 2.5
t
35Minute＞31 8.5＞31 4.5
Test-results shows, at 8 week back t
5And t
35Cross non-irrigated curing time and do not demonstrate any tangible difference, this shows to have good preservation stability.
Embodiment 2
Present embodiment is the stability in storage that is used for further specifying vulcanisable compound.With the Banbury closed mixing machine following component is mixed down in room temperature (25 ℃).
Component is based on 100 weight parts per hour
Polyacrylic rubber 100
Stearic acid 1
N550，EFE 65
Agerite Stalite S 2
Sodium stearate 4
CETRIMIDE POWDER 1
With two-roller mill the composition mixing after, be determined at mooney viscosity under 85 ℃, 100 ℃ and 125 ℃ with ectotrochanter.At room temperature wore out for 8 weeks, every getting corresponding mooney viscosity data 2 weeks.In addition, also under 190 ℃ and 3 radians, carry out the test of mobilometer oscillating plate, noted smallest point (M
L), maximum point (M
HF) and sulfuration point (t
90) do not stipulate the latter here, with identical test parameter), test-results is as follows.
Mooney viscosity (ectotrochanter)
Test week 02468
85℃
MV minium viscosity 73 65---
t
5, minutes 27＞30---
t
35, minute＞＞30＞＞30---
100℃
MV minium viscosity 60 52 56 55 56
t
5, minutes 8.0 8.0 9.5 9.0 9.5
t
35, minutes 13.3 13.5 16.5 15.0 15.5
125℃
MV minium viscosity 51 45---
t
5, minutes 2.5 2.5---
t
35, minutes 3.5 3.5---
The miniature mould of mobilometer, 100 cycle per minute clocks, 3 radians, 190 ℃
M
LFt lbf-inch 7.5
M
HFFt lbf-inch 61.8
t
' 90Minutes 3.8
Embodiment 3
Present embodiment is to be used for illustrating that many quaternary ammonium salt Huo quaternary alkylphosphonium salts that contain fontanel element or oxyhydroxide active group have temperature sensitivity (promptly be lower than under the ultimate temperature have stability in storage), have good machinery and compression set character and do not need postcure but can be sulfided into, just sulfuration will be carried out in temperature range limit.
The prescription deal of master batch
Contain the plain and two sulfuration point of carboxyl 100 weight parts of fontanel
Polyacrylic rubber
Stearic acid (lubricant and retarding agent) 1
Sturktol WB-222(fat soap,
Processing material) 2
Rhiblack N550(carbon black, filler) 65
Stalite S(octylated diphenylamine,
Antioxidant) 2
With Banbury banburying machine with the master batch mixing.Make 400 gram master batchs and 9.4 gram (4 parts) sodium stearate and 2.35 gram (being equivalent to 1 part in per 100 parts of polymkeric substance) CETRIMIDE POWDER blend then.Replace bromohexadecane base TMA (TriMethylAmine) with other vulcanizing agent shown in following.Use all vulcanizing agents by identical molar weight.Therefore, according to the molecular weight of vulcanizing agent, for CETRIMIDE POWDER, its consumption is 1 part of per 100 parts of rubber, and following vulcanizing agent will be used this amount scarcely.
Used vulcanizing agent has:
1. CETRIMIDE POWDER,
2. TBAC tetrabutylammonium chloride,
3. bromination tetrabutylammonium,
4. tetrabutylammonium iodide,
5. Xiuization Si Ben Phosphonium,
6. bromination Shi six alkyl San Ding Phosphonium,
7. tetramethylammonium hydroxide pentahydrate,
8. bromination hexadecyl methyl second ammonium,
9. Lvization Si Ben Phosphonium,
10. iodate Si Ben Phosphonium,
11. Lvization Si Ding Phosphonium,
12. Xiuization Si Ding Phosphonium,
13. tosic acid hexadecyl TMA (TriMethylAmine),
14. tetradecyl trimethylammonium bromide.
Vulcanizing agent and master batch one mix, and carry out the miniature mould vibrating disk test of mobilometer under 100 cycle per minute clocks, 190 ℃ and 3 radians immediately.With smallest point (M), maximum point (M) and the sulfuration point (t) (time when being change in torque 90%) that obtains and note 14 kinds of vulcanizing agent system.In addition, also be determined at mooney viscosity under 100 ℃ and 125 ℃ and t and t(minute).The result of these tests is as shown in the table.
Can obviously find out have the vulcanization rate of some vulcanizing agents faster than other from above all embodiment.The fast vulcanizing agent of vulcanization rate can use with inhibitor, and to increase curing time, making has long process period.Those have the vulcanizing agent of longer process period, and its time spent can be bigger than the consumption of present embodiment, so that can shorten some process periods.According to above data, can know and find out, can be with several different vulcanizing agents, can be controlled process period by the consumption that uses inhibitor or increasing or reduce vulcanizing agent itself.
Embodiment 4
The original physical properties of cited all cpds is as shown in the table among the embodiment 3.Physical properties be used in 190 ℃ down 4 minutes samples of sulfuration record, the compression set data record after following 70 hours at 150 ℃.The first row physical properties of enumerating in the table is 100% o'clock a tensile stress of elongation, and the required strength (stress) of per unit area when expression is elongated original length 100% with sulfide polymer is pressed ASTM D412 method and measured.The physical properties of second row is maximum fracture tensile strength, and the third line physical properties is the extension at break degree, presses ASTM D412 method and measures.The fourth line physical properties is a hardness, and it is legal to press ASTM D2240.Last column physical properties is the overlapping compression set, measures according to ASTM D395 B method.
Cross drought sulfuration data, aging data and original physical properties according to rheological data, Mooney, CETRIMIDE POWDER can be the master batch goods character that the most all claims is provided.Moreover, owing in order to prevent the drought sulfuration and to vulcanize in advance and use inhibitor etc., still can make these change of properties.
Embodiment 5
Go definite Mooney to cross the relation of non-irrigated curing time and temperature with CETRIMIDE POWDER.The MV minium viscosity under differing temps of measured CETRIMIDE POWDER, t
5Value, t
35Value and 31 minutes the time viscosity as shown in the table.
Mooney viscosity, ectotrochanter
Temperature, ℃ 70 80 85 90 93 100 125
MV minium viscosity 81.0 71.6 60.3 54.9 58.0 54.7 46.7
t
5, minute＞31＞31＞31 22.8 22.8 8.7 2.8
t
35, minute＞31＞31＞31＞31＞31 15.1 3.7
Viscosity 81.0 72.0 62.2 67.0 84.2 in the time of 31 minutes
According to above result, in being mixed with the master batch batching of 1 part of inhibitor, CETRIMIDE POWDER begins sulfuration in about 85～90 ℃ scope of temperature.Be lower than this scope,, show essentially no activity as the CETRIMIDE POWDER of vulcanizing agent.Replace CETRIMIDE POWDER to do similar test with the tetramethylammonium hydroxide pentahydrate.Measured MV minium viscosity, t
5Value, t
35Value and 31 minutes the time viscosity as shown in the table.
Mooney viscosity, ectotrochanter
Temperature, ℃ 75 80 85 100 125
MV minium viscosity 71 66 62 59 56
t
5, minutes-22.2 15.9 5 1.8
t
35, minutes---8.8 2.3
Viscosity 74 74 76 in the time of 31 minutes--
According to top result, the ultimate temperature during the sulfuration beginning is tangible.The standard of vulcanizing temperature range when beginning is that the mooney viscosity after 31 minutes raises 5 or bigger.The ultimate temperature of elite vulcanizing agent is as follows.
The vulcanizing agent temperature range limit, ℃
Xiuization Si Ben Phosphonium 80～85
Tetramethylammonium hydroxide pentahydrate 75～80
Cetyldimethylethylammonium bromide 80～85
Lvization Si Ben Phosphonium 75～80
Embodiment 6
Carry out the embodiment test with the method identical and prescription with CETRIMIDE POWDER, just with potassium stearate place of magnesium stearate sodium with embodiment 3.
The result is as follows.
Mobilometer (100 cycle per minute clocks, 190 ℃, 3 radians) M
L8.8
M
HF54.1
t
' 90(minute) 5.2
Mooney viscosity (ectotrochanter)
100 ℃ of MV minium viscosity 50
t
5, minutes 5.5
t
35, minutes 10.0
Compression set (150 ℃ and overlap following 70 hours), % 37
Embodiment 7
The following examples are to be used for illustrating a component vulcanizing agent system.To have the master batch that is equivalent to embodiment 3 used prescriptions (just not adding stearic acid) with the Banbury closed mixing machine mixes.By the amount of 2 parts of stearic acid tetrabutylammoniums of per 100 parts of polyacrylic ester, it is added in the master batch.Under 125 ℃, measured the Mooney viscosity of sample with ectotrochanter.Under 100 cycle per minute clocks, 190 ℃ and 3 radians, carried out the oscillating plate test of mobilometer with miniature mould.To measuring in the physical properties of the sample of sulfuration after 4 minutes under 190 ℃.In addition, also to measuring at the compression set of 150 ℃ of sulfuration samples after following 70 hours.Test-results is as follows.
Mooney's viscosimeter, ectotrochanter, 125 ℃
MV minium viscosity 73
t
5, minutes 1.6
t
35, minutes 2.0
Mobilometer, miniature mould, 100 cycle per minute clocks, 3 radians, 190 ℃
M
L, ft lbf-inch 14.5
M
HF, ft lbf-inch 52.5
t
' 90, minutes 16.5
Original physical properties is after vulcanizing 4 minutes under 190 ℃
M100, pound/square inch 400
The breaking limit tensile strength, pound/square inch 1700
Ultimate elongation, % 300
Hardness (sclerometer A) 60
Compression set, (150 ℃ and overlapped following 70 hours), % 80
This shows that method provided by the present invention has reached above-mentioned target fully and had above-mentioned advantage.Though invention has been described in conjunction with specific embodiment, obviously, the professional who is familiar with present technique can propose many other schemes, improvement and variation by above explanation.Therefore, all other schemes, improvement and variation all are included in spirit of the present invention and the broad scope.
Claims (25)
1, a kind of polyacrylic rubber sulfurized vulcanization process without issue that contains fontanel element and the two sulfuration points of carboxyl that makes comprises:
The vulcanizing agent of significant quantity is mixed with the described fontanel polyacrylic rubber plain and the two sulphur centers of carboxyl that contains, and till obtaining uniform vulcanisable compound, described vulcanizing agent is selected from the stearate of quaternary ammonium Huo quaternary phosphine;
Can make the described composition of the basic sulfurized activation temperature of described composition scope internal heating, thereby not need to carry out postcure.
2, the described method of claim 1, be included in and be lower than another storing step that stores above-mentioned composition under the above-mentioned activation temperature scope, this step is before the above-mentioned mixing step and after above-mentioned heating steps, and this storing step can not damage the stability in storage of above-mentioned composition.
3, the described method of claim 1, wherein said acrylic elastomer comprises: (a) about 40～99.8%(weight) acrylate that is shown below:
R is selected from by the alkyl that contains 1～18 carbon atom, alkoxyalkyl, alkane alkylthio and contains the group that the cyano group alkyl of 2～12 carbon atoms is formed in the formula; (b) 0.1～30%(weight) contain the plain monomer of fontanel, this monomer be selected from by the ethylene hydro carbons that contains the fontanel element and have at least 2 carbon atoms that separate with the oxygen base the fontanel base contain the group that fontanelle ethylene base monomer is formed; (c) about 0.1～20%(weight) contain carboxylic monomer; (d) up to 35%(weight) contain the copolymerisable monomer of vinylidene end group.
4, the described method of claim 3, wherein said acrylic elastomer comprises: (a) about 65～99.6%(weight) acrylate, wherein R is selected from the group that alkyl that contains 1～10 left and right sides carbon atom and the alkoxyalkyl that contains 2～8 left and right sides carbon atoms are formed; (b) about 0.2～15%(weight) contain the plain monomer of fontanel; (c) about 0.2～10%(weight) contain carboxylic monomer; (d) up to 10%(weight) about contain the copolymerisable monomer of vinylidene end group.
5, the described method of claim 4, (a) wherein is selected from the group of being made up of ethyl propenoate, butyl acrylate, vinylformic acid methoxy ethyl ester and vinylformic acid ethoxy ethyl ester; (b) be selected from the group that Mono Chloro Acetic Acid vinyl ester, Mono Chloro Acetic Acid allyl ester, vinylformic acid 2-chloroethene ester, 2-chloroethyl vinyl ether, vinyl chloride, 5-chloromethyl-2-norbornylene and 5-Mono Chloro Acetic Acid ylmethyl-2-norbornylene is formed, (c) be selected from the group formed by vinylformic acid, methacrylic acid and methylene-succinic acid and (d) be selected from the group of forming by vinyl-acetic ester, methyl methacrylate, Jia Jibingxisuanyizhi, vinylbenzene, vinyl cyanide, acrylamide and diethylene glycol diacrylate.
6, the described method of claim 1, wherein said vulcanizing agent comprises the stearate of quaternary ammonium Huo quaternary phosphine, and the amount of this salt is about 0.1～25 weight parts of per 100 parts by weight of rubber, and the structural formula of this salt is:
Q is nitrogen or phosphorus in the formula; R
1, R
2, R
3And R
4For containing the alkyl of 1～18 left and right sides carbon atom, for example alkyl, aryl, alkaryl and aralkyl; Or R
1, R
2, R
3And R
4In 2 or 3 form with nitrogen or phosphorus atom and to contain 3～8 heterocycle structures that select the atom of the group that free carbon, nitrogen, oxygen and sulphur forms, having 2 atoms in the structure at least is carbon atoms; RCOO-is a stearate ion.
7, the described method of claim 6, the stearate of wherein said quaternary ammonium Huo quaternary phosphine are to be selected from the group of being made up of stearic acid benzyl trimethyl ammonium, stearic acid San Jia Ji Bian Phosphonium, stearic acid trimethylammonium soya-bean oil base (soya) ammonium, stearic acid trimethylammonium soya-bean oil Ji Phosphonium, stearic acid tetramethylammonium, stearic acid Si Jia Phosphonium, stearic acid hexadecyl TMA (TriMethylAmine), stearic acid Shi six Wan base San Jia Phosphonium, stearic acid dimethylbenzyl ammonium and stearic acid Er Jia Ji Bian Phosphonium.
8, a kind of Yan, a state in the Zhou Dynasty ┧ marmoset Ha mythical bird like the phoenix milli a red-spotted lizard moss crack a red-spotted lizard green pepper ǎ ǎ how that contains the two sulfuration points of fontanel element and carboxyl that makes
The vulcanizing agent of significant quantity is mixed with the described fontanel polyacrylic rubber plain and the two sulfuration points of carboxyl that contains, till obtaining uniform vulcanisable compound, above-mentioned vulcanizing agent comprises the stearate and the quaternary salt of metal, and this quaternary salt is selected from the plain salt of fontanel by the hydroxide salt, quaternary phosphine of the plain salt of the fontanel of quaternary ammonium, quaternary ammonium with the group that the hydroxide salt of quaternary phosphine is formed; With
Can make the described composition of the basic sulfurized activation temperature of described composition scope internal heating, thereby not need to carry out postcure.
9, the described method of claim 8, also be included in and be lower than the storing step that stores above-mentioned composition under the above-mentioned activation temperature scope, this step is after above-mentioned mixing step and before the above-mentioned heating steps, and this storing step can not damage the stability in storage of above-mentioned composition.
10, the described method of claim 8, wherein said acrylic elastomer comprise (a) about 40～99.8%(weight) acrylate that is shown below:
R is selected from by the alkyl that contains 1～18 carbon atom, alkoxyalkyl, alkane alkylthio and contains the group that the cyano group alkyl of 2～12 carbon atoms is formed in the formula; (b) about 0.1～30%(weight) contain the plain monomer of fontanel, this monomer be selected from by the ethylene hydro carbons that contains the fontanel element and have at least 2 carbon atoms that separate with the oxygen base the fontanel base contain the group that fontanelle ethylene base monomer is formed; (c) about 0.1～20%(weight) contain carboxylic monomer; (d) up to 35%(weight) contain the copolymerisable monomer of vinylidene end group.
11, the described method of claim 10, wherein said acrylic elastomer comprises: (a) about 65～99.6%(weight) acrylate, and wherein R is selected from the group of being made up of alkyl that contains 1～10 left and right sides carbon atom and the alkoxyalkyl that contains 2～8 left and right sides carbon atoms; (b) about 0.2～15%(weight) contain the plain monomer of fontanel; (c) about 0.2～10%(weight) contain carboxylic monomer; (d) up to 10%(weight) about contain the copolymerisable monomer of vinylidene end group.
12, the described method of claim 11, (a) wherein is selected from the group of being made up of ethyl propenoate, butyl acrylate, vinylformic acid methoxy ethyl ester and vinylformic acid ethoxy ethyl ester; (b) be selected from the group that Mono Chloro Acetic Acid vinyl ester, Mono Chloro Acetic Acid allyl ester, vinylformic acid 2-chloroethene ester, 2-chloroethyl vinyl ether, vinyl chloride, 5-chloromethyl-2-norbornylene and 5-Mono Chloro Acetic Acid ylmethyl-2-norbornylene is formed, (c) be selected from the group formed by vinylformic acid, methacrylic acid and methylene-succinic acid and (d) be selected from the group of forming by vinyl-acetic ester, methyl methacrylate, Jia Jibingxisuanyizhi, vinylbenzene, vinyl cyanide, acrylamide and diethylene glycol diacrylate.
13, the described method of claim 8, wherein said vulcanizing agent contains quaternary salt, and the amount of this salt is about 0.5～25 weight parts of per 100 parts by weight of rubber, and the structural formula of this salt is:
In the formula: Q is nitrogen or phosphorus; R
1, R
2, R
3And R
4For containing the alkyl of 1～18 left and right sides carbon atom, for example alkyl, aryl, alkaryl and aralkyl; Or R
1, R
2, R
3And R
4In 2 or 3 form with nitrogen or phosphorus atom and to contain 3～8 heterocycle structures that select the atom of the group that free carbon, nitrogen, oxygen and sulphur forms, it is carbon atoms that structure has 2 atoms at least; X is an ion, for example chlorine (Cl
-), bromine (Br
-), iodine (I
-) or oxyhydroxide (OH).
14, the described method of claim 8, the stearate of wherein said metal is selected from sodium stearate or potassium stearate.
15, the described method of claim 13, wherein said quaternary ammonium salt is selected from by tetramethylammonium chloride, tetramethylammonium bromide, iodate trimethylammonium second ammonium, chlorination trimethylammonium soya-bean oil base (soya) ammonium, bromination trimethylammonium cetyltrimethyl ammonium, the chlorination benzyl trimethyl ammonium, chlorination trimethylammonium cetyltrimethyl ammonium, chlorination dimethyl octyl group benzyl ammonium, chlorination dimethyl oil base (oley) benzyl ammonium, chlorination dimethyl stearyl benzyl ammonium, bromination 3,5-dimethylphenyl benzyl ammonium, bromination dimethyl dibenzyl ammonium, methyl chloride ethyl propyl isobutyl ammonium, Tetradecyltrimethylammonium chloride, Diethylaminoethyl hexadecyl dibenzyl ammonium, cetylpyridinium chloride, brocide, TBAC tetrabutylammonium chloride, the bromination tetrabutylammonium, tetrabutylammonium iodide, the earnest of hydrogen-oxygen collect alms crime Hou rank an ancient spear awake hazel unravels silk the stupid mire spinulose tree fern of the curved awake of anti-hazel crime ё mallet of А ⒑
16, the described method of claim 13, wherein said quaternary alkylphosphonium salt are selected from the group of being made up of Xiuization Si Ben Phosphonium, bromination Shi six alkyl San Ding Phosphonium, Lvization Si Ben Phosphonium, iodate Si Ben Phosphonium, Lvization Si Ding Phosphonium, Xiuization Si Ding Phosphonium, chlorinated triphenyl Bian Phosphonium, bromination triphen Bian Phosphonium, iodate triphen Bian Phosphonium, chlorinated triphenyl Jia Yang Jia Phosphonium, Lvization San Yi Ji Bian Phosphonium and chlorination thricyclohexyl Bian Phosphonium.
17, a kind of polyacrylic rubber sulfurized vulcanization process without issue that contains fontanel element and the two sulfuration points of carboxyl that makes comprises:
The vulcanizing agent of significant quantity is mixed with the described fontanel polyacrylic rubber plain and the two sulfuration points of carboxyl that contains, till obtaining uniform hardenable composition, above-mentioned vulcanizing agent is selected from the carboxylate salt that contains 2～24 left and right sides carbon atoms of quaternary ammonium Huo quaternary phosphine and the group that structural formula organophosphate as follows is formed
（R-O）zPOyM
M is a quaternary ammonium Huo quaternary phosphine in the formula, and Y equals 1 or 2, and Z equals 1 or 2, and Y adds Z and equals 3, and R is selected from the group of being made up of alkyl that contains 1～24 left and right sides carbon atom and the aryl that contains 6～24 left and right sides carbon atoms;
Can make the described composition of activation temperature scope internal heating of the basic sulfo-of described composition, thereby not need to carry out postcure.
18, a kind of polyacrylic rubber sulfurized vulcanization process without issue that contains fontanel element and the two sulfuration points of carboxyl that makes comprises:
The vulcanizing agent of significant quantity is mixed with the described fontanel polyacrylic rubber plain and the two sulfuration points of carboxyl that contains, till obtaining uniform vulcanisable compound, above-mentioned vulcanizing agent contains the hydrochlorate and the quaternary salt of metal, and the hydrochlorate of this metal is selected from the group of being made up of the metal-salt of the metal-salt of the carboxylic acid that contains 2～24 left and right sides carbon atoms and structural formula organic phosphoric acid as follows.
（R-O）zPOyM
M is a basic metal in the formula, Y equals 1 or 2, Z equals 1 or 2, Y adds Z and equals 3, R is selected from the group of being made up of alkyl that contains 1～24 left and right sides carbon atom and the aryl that contains 6～24 left and right sides carbon atoms, above-mentioned quaternary salt is selected from the quaternary ammonium salt Huo quaternary alkylphosphonium salt that negatively charged ion is X, and X is the negatively charged ion of organic acid or mineral acid, and the acidic hydrogen in the acid links to each other with fontanelle atom or Sauerstoffatom;
Can make the described composition of the basic sulfurized activation temperature of described composition scope internal heating, thereby not need to carry out postcure.
19, the described method of claim 18, X wherein is selected from by Cl
-, Br
-, I
-, HSO
- 4, H
2PO
- 4, RCOO
-, ROSO
- 3, RSO
- 3And ROPO
3H
-The group of forming, R wherein is alkyl or the alkaryl that contains 1～18 carbon atom.
20, a kind of polyacrylic rubber sulfurized vulcanization process without issue that contains fontanel element and the two sulfuration points of carboxyl that makes comprises:
The vulcanizing agent of significant quantity is mixed with the described fontanel polyacrylic rubber plain and the two sulfuration points of carboxyl that contains, till obtaining uniform vulcanisable compound, this vulcanizing agent is selected from the quaternary ammonium salt Huo quaternary alkylphosphonium salt of the following organic phosphoric acid of the quaternary ammonium salt Huo quaternary alkylphosphonium salt of the carboxylic acid that contains 2～24 left and right sides carbon atoms and structural formula
（R-O）zPOyM
In the formula, M is a quaternary ammonium Huo quaternary phosphine, Y equals 1 or 2, Z equals 1 or 2, Y add Z equal 3 and R be selected from the group of forming by the aryl of the alkyl that contains 1～24 left and right sides carbon atom and 6～24 left and right sides carbon atoms, said mixture has the ultimate temperature characteristic, this ultimate temperature characteristic comprises temperature range limit, the time t that promptly uses mooney's viscosimeter ectotrochanter test method(s) (ASTM D1646) to record
5Value raise 5 or the temperature when bigger; With
Can make the described composition of the basic sulfurized activation temperature of described composition scope internal heating, thereby not need to carry out postcure.
21, the described method of claim 20, what wherein said ultimate temperature characteristic comprised that low MV minium viscosity changes (aged at room temperature record after 2 weeks 100 ℃ times viscosity change be lower than 150 mooney units) does not vulcanize first scope, sulfurized second scope and vulcanising composition complete cure in temperature range limit (with ASTM test method(s) D395 record 150 ℃ and overlap under compression set after 70 hours be equal to or less than 80%) the 3rd sulfuration scope.
22, the described method of claim 21, wherein said low MV minium viscosity changes does not vulcanize first scope, viscosity change is lower than 5 mooney units when being aged at room temperature record after 8 weeks 100 ℃, and the compression set that above-mentioned the 3rd sulfuration scope is vulcanized when complete is equal to or less than 40%.
23, a kind of polyacrylic rubber sulfurized vulcanization process without issue that contains fontanel element and the two sulfuration points of carboxyl that makes, comprise: the vulcanizing agent of significant quantity is mixed with the described fontanel polyacrylic rubber plain and the two sulfuration points of carboxyl that contains, till obtaining uniform vulcanisable compound, above-mentioned vulcanizing agent comprises the salt and the quaternary salt of metal, the hydrochlorate of this metal is selected from the group of being made up of the salt of the following organic phosphoric acid of the salt that contains 2～24 left and right sides carbon atom carboxylic acids and structural formula
（R-O）zPOyM
M is a basic metal in the formula, Y equals 1 or 2, z equals 1 or 2, Y add z equal 3 and R be selected from by the alkyl that contains 1～24 left and right sides carbon atom and contain the group that the aryl of 6～24 left and right sides carbon atoms is formed, above-mentioned quaternary salt is selected from the quaternary ammonium salt Huo quaternary alkylphosphonium salt that negatively charged ion is X, X is the plain atom of acidic hydrogen and fontanel or Sauerstoffatom link to each other in the acid the organic acid or the negatively charged ion of mineral acid, above-mentioned composition has the ultimate temperature characteristic, this ultimate temperature characteristic comprises temperature range limit, the time t that promptly uses mooney's viscosimeter ectotrochanter test method(s) (ASTMD1646) to record
5Value in 31 minutes, raise 5 or the temperature range when bigger; With
Can make the described composition of the basic sulfurized activation temperature of described composition scope internal heating, thereby not need to carry out postcure.
24, the described method of claim 23, what wherein said ultimate temperature characteristic comprised that low MV minium viscosity changes (aged at room temperature record after 2 weeks 100 ℃ times viscosity change be lower than 150 mooney units) does not vulcanize first scope, sulfurized second scope and vulcanising composition complete cure in temperature range limit (with ASTM test method(s) D395 record 150 ℃ and overlap under compression set after 70 hours be equal to or less than 80%) the 3rd sulfuration scope.
25, the described method of claim 23, wherein said low MV minium viscosity changes does not vulcanize first scope, viscosity change is lower than 5 mooney units and above-mentioned the 3rd sulfuration scope and vulcanizes that measured compression set is equal to or less than 40% when complete when being aged at room temperature record after 8 weeks 100 ℃.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10188387A | 1987-09-28 | 1987-09-28 | |
| US101,883 | 1987-09-28 | ||
| US22739688A | 1988-08-04 | 1988-08-04 | |
| US227396 | 1988-08-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1032444A true CN1032444A (en) | 1989-04-19 |
Family
ID=26798747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88106893A Pending CN1032444A (en) | 1987-09-28 | 1988-09-27 | Make polyacrylate polymers sulfurized vulcanization process without issue |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0309794B1 (en) |
| JP (1) | JP2834149B2 (en) |
| KR (1) | KR960006796B1 (en) |
| CN (1) | CN1032444A (en) |
| AU (1) | AU619483B2 (en) |
| BR (1) | BR8804992A (en) |
| CA (1) | CA1339230C (en) |
| DE (1) | DE3856123T2 (en) |
| MX (1) | MX169033B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153895B2 (en) * | 2001-09-12 | 2006-12-26 | Uniroyal Chemical Company, Inc. | Blending of rubber compounds, fillers and plasticizers |
| US7825200B2 (en) * | 2003-02-28 | 2010-11-02 | The Regents Of The University Of California | Controlled free radical grafting from polyolefins |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912672A (en) * | 1972-07-18 | 1975-10-14 | Goodrich Co B F | Acrylate rubber vulcanizable compositions |
| US3875092A (en) * | 1973-09-17 | 1975-04-01 | Goodrich Co B F | Acrylate rubber vulcanizable compositions |
| US3925281A (en) * | 1974-06-05 | 1975-12-09 | Goodrich Co B F | Vulcanizable acrylate rubber compositions |
| JPS6054976B2 (en) * | 1983-06-09 | 1985-12-03 | 大阪曹達株式会社 | Halogen-containing polymer vulcanization composition |
-
1988
- 1988-09-09 AU AU22080/88A patent/AU619483B2/en not_active Ceased
- 1988-09-09 DE DE3856123T patent/DE3856123T2/en not_active Expired - Lifetime
- 1988-09-09 EP EP88114787A patent/EP0309794B1/en not_active Expired - Lifetime
- 1988-09-21 CA CA000578034A patent/CA1339230C/en not_active Expired - Fee Related
- 1988-09-22 MX MX013104A patent/MX169033B/en unknown
- 1988-09-24 KR KR1019880012390A patent/KR960006796B1/en not_active IP Right Cessation
- 1988-09-27 JP JP63239886A patent/JP2834149B2/en not_active Expired - Lifetime
- 1988-09-27 BR BR8804992A patent/BR8804992A/en not_active IP Right Cessation
- 1988-09-27 CN CN88106893A patent/CN1032444A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0309794A3 (en) | 1989-07-19 |
| AU619483B2 (en) | 1992-01-30 |
| KR960006796B1 (en) | 1996-05-23 |
| JPH01163248A (en) | 1989-06-27 |
| JP2834149B2 (en) | 1998-12-09 |
| CA1339230C (en) | 1997-08-05 |
| EP0309794A2 (en) | 1989-04-05 |
| DE3856123D1 (en) | 1998-03-05 |
| EP0309794B1 (en) | 1998-01-28 |
| BR8804992A (en) | 1989-05-02 |
| KR890005180A (en) | 1989-05-13 |
| AU2208088A (en) | 1989-04-06 |
| MX169033B (en) | 1993-06-17 |
| DE3856123T2 (en) | 1998-06-10 |
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